Abstract: It is important to understand the existing forms of organonitrogen compounds in coal and subsequently to choose proper approaches for removing and utilizing the components. The tetrahydrofuran/methanol-insoluble fraction (residue) was obtained by solvent extraction from Datong bituminous coal, then noncatalytic and metal (Fe, Ni and Pd/C)-catalyzed thermolysis of the residues were conducted in cyclohexane under pressurized hydrogen at 300 ℃. Petroleum ether-soluble fractions from thermolysis products were identified with GC/MS. The results showed that organonitrogen can be released from the residues in metal (especially Ni and Pd/C)catalyzed thermolysis. The detected compounds are predominantly aniline and its alkylsubstituted derivatives. The metal-catalyzed hydrogenation of polycyclic aromatic rings in coal destroyed both intermolecular interactions and covalent bonds so that the organonitrogen compounds could be released from macromolecule network.